Monoazo dyestuffs



Patented Mar. 4, 1941 UNITED STATES PATENT OFFICE MONOAZO DYESTUFFS Wilfrid Herbert Clifie and Arthur Howard Knight, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain N0 Drawing. Application May 18, 1938, Serial No. 208,708. In Great Britain May 26, 1937 9 Claims.

R NH:

(wherein R1 can be an alkyl radical and R2 an aromatic radical) with N-acylated derivatives of peri-amino-naphthol-disulfonic acids containing an aryl-oxy fatty acid radical, R1, as alkyl, being exemplified by methyl, ethyl, nbutyl, lsobutyl, isoamyl, and isohexyl, but these colors lack washing fastness.

It is an object of the invention to produce dyes similar to those described in the identified British patents but superior in washing and milling fastness to the colors of the first of saidpatents and superior in washing fastness to the colors of the second of said patents.

According to the present invention we manufacture the new dyestuffs by combining the diazo compounds of aromatic amines of the general formula:

wherein X means a long chain aliphatic hydrocarbon radical of at least 10, not more than 20 carbon atoms (and preferably 10 to 16 carbon atoms), and Y means an aryl radical of the benzene series, with coupling components devoid of long chain aliphatic hydrocarbon radicals and which are naphthol-dior tri-sulfonic acids, N-acidyl-l B-amino-naphtholdisulfonic acids or sulfo-aryl-pyrazolones.

The dyes of the present invention are distinguished from the known ones mentioned in the first said patent by yielding Wool dyeings of superior fastness to severe washing and milling. The analogous dyestuffs of the present invention are superior to the known dyestuifs of British specification No. 462,940 in fastness to severe washing.

The diazo components employed according to the present invention may be obtained for example by condensing the corresponding secondary amines with a nitro-aroyl chloride and reducing the condensation products obtained. The new dyestuffs obtained according to the present in- 30 vention yield shades on wool ranging fromyellow to orange to bluish red. They can be conveniently applied to the fiber from a dyebath containing 2% ammonium acetate. The colorations are characterized by possessing excellent fastness to severe washing and milling and very good light fastness.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example I A mixture of 38 parts of 3-aminobenz-N-dodecyl-anilide, (m. p. 63 C.), 500 parts of water and 25 parts of 36% hydrochloric acid is heated The base is then diazotized by the .addition of 6.9 par-ts of sodium nitrite, the diazo compound being obtained in solution. The diazo solution, after filtration if necessary, is then cooled to 5 C. and added to a similarly cooled solution of 30.4 parts of 2-naphthol-6z8-disulfonic acid in 400 parts of water containing suflicient sodium carbonate to keep the coupling alkaline to litmus. When coupling is complete the dyestufi is isolated by adding 5% sodium chloride (weight for volume), filtering and drying.

The new dyestufi forms a bright orange powder, which dissolves in water to a yellowish solution. It dyes wool from an acid bath or from a bath containing 2% of ammonium acetate in yellowish-orange shades of excellent fastness to severe washing, milling, and light.

Example II A fine suspension of 38 parts of 4-aminobenz- N-dodecyl-anilide (m. p. 69 C.) in a mixture of 350 parts of water and 25 parts of 36% hydrochloric acid is diazotized by adding 6.9 parts of 7 sodium nitrite. The diazo solution so obtained is filtered if necessary and added to a cooled solution (5 C.) of 25.4 parts of 1-(4'.-sulfophenyl)- 3-methyl-5-pyrazolone in 400 parts of water containing sufiicient sodium carbonate to keep the coupling mixture alkaline to litmus. The dyer stuff is isolated as in Example I. It forms a yellow powder which dissolves in water to a yellow solution, and dyes wool in pure yellow shades of excellent fastness to severe washing, milling, and light when applied as in Example I.

If, in the above example, instead of 25.4 parts of 1-(4- sulfophenyl) 3 methyl 5 pyrazolone there are used 32.3 parts of 1-(2' :5'-dichloro-4'-- sulfophenyl)-3-methyl-5-pyrazolone, the resulting dyestufi dyes wool in greener shades of yellow of similar fastness properties.

Example III Example IV '38 parts of 3-amino-benz-N-dodecyI-anilide are diazotized as in Example I and the solution of the diazo compound so obtained is added'to a cold solution 'of 49 parts of 1-(2'-chlorophenoxy acetyl amino) 8 naphthol 4:6

disulfonic acid in'600 parts of water containing.

sufficient sodium'carbonate to keep the coupling mixture alkaline to litmus. The new dyestufi forms a'reddish powder, soluble in hot water to a red solution, and dyes wool in scarlet shades of very good fastness to severe washing and milling, and good fastness to light.

If in the above example instead of 38 partsof 3-aminobenz-N-dodecylanilide there are used 39.4 parts of 4-aminobenz-N-dodecy1-2-to1uidide a dyestufl is obtained which yields rather redder shadesonwool of thesame good iastness properties.'-

to 80 C. and then cooled to 15 C. with stirring.

Example V A finely divided suspension of 45.1 parts of the hydrochloride of 4-aminobenz-N-dodecyl-2'- chloro-anilide in 400 parts of water containing 15. parts of 36% hydrochloric acid is diazotized by the addition of 6.9 parts of sodium nitrite. The solution of the diazo compound, after filtration if necessary, is cooled to 5-10 C. and added to a cooled aqueous solution of 30.4 parts of l-naphthol-SzG-disulfonic acid containing excess of sodium carbonate. Coupling is rapid. The new dyestufl is isolated by the addition of 5% common salt (weight for volume), filtering, and drying. It dyes wool in reddish-orange shades of very good fastness to severe washing and milling. v

If in the above example instead of 30.4 parts of 1-naphthol-3:6-disulfonic acid there are employed 32.3 parts of 1-(2':5-dichloro-4-sulfophenyl) -3-methyl-5-pyrazolone a dyestufi is obtained which dyes wool in greenish-yellow shades of very good fastness to severe washing, milling,

and light.

Example VI A finely divided suspension of 47.3 parts of the hydrochloride of 3-aminobenz-N-cetyl-anilide in 350 parts of. water containing 15 parts of 36% hydrochloric acid is diazotized by the addition of 6.9 parts of sodium nitrite. The suspension of the diazo compound so obtained is cooled to 5-10 C. and added to a cooled aqueous solution of 38.4 parts of 1-naphthol-3:6:B-trisulfonic acid containing excess of sodium carbonate. The new dyestufi is filtered off anddried. It dyes wool in" orange-brown shades of very good "fastness' to severe washing, milling and light.

Example VII 41 parts of 3amino-4-methoxybenz-N-dodecyl-anilide are suspended in 450 parts of water containing 25 parts of 36% hydrochloric acid. The suspension is heated to C. and the thick syrup so obtained then cooled to 25 C., 7.0 parts of sodium nitrite are then added, the diazo com pound thereby formed remaining in solution. This solution is cooled to 5-10 C. and added to a cooled aqueous solution of-47.3 parts of 1-p-' toluene-sulfonyl-amino-8-naphthol-3 6-disulfon-' Example VIII 39.4 parts of 3,-aminoA-methylbenz-NFdm decyl-anilide are suspended in 500 parts of water containing 25 parts of 36% hydrochloric acid. The suspension is heated to 75 C. and the thick syrup thus obtained cooled to 20. 25 C'.l 7 parts of sodium nitrite are then added, theidiazo compound thereby formed remaining in jjsolution. This solution is cooled. to 5-10" C. and added to. a cooled aqueous solution of. 30.4 "parts ofl-naphthol-3z8-disulfonic acid containing", excess of 50- dium carbonate. The new dyestufilis' isolated by.

adding 5% common salt (weighl lfp f Volume), filtering and drying. ltjdyesj'wool in reddishe,

orange shades of excellentfias'tness,-toll'severe washingand milling... L

The invention is further illustrated by the examples listed in the following table:

ample Diazo component Coupling component Shade on wool number 9 B-aminobenz-N-dodecyl-anilide 1-(fi'zy-dichloro-y-suliophenyl)-3-methyl-5-pyraz- Greenish-yellow. one. 3-3:}lillJ-4-Hl6th0XYb8l1Z -N-dodecyldo Yellow.

a l e. 10 ll 3-aminobenz-N-dodecyl-anilide l-(4-sulfophenyl)-3-methyl-5-pyrazolone Yellow.

12 3-aininii-4-methoxybenz-N- dodecyll-(4-sulfophenyl)-3-methyl-5-pyrazolone. Reddish-yellow.

am: e. 13 i-arginobenz-N-dodecyl-W-chloro-anido Yellow.

1 e. l4 3-aminobenz-N-dodecyl-anilide 1-naphtho1-316:8-trisulfonic acid Reddlsh-orange. 15 4-aminobenz-N-dodecy]-anilide l-naphthol-ii:6z8-trisu1tonicacid Yellowish-scarlet. 1 16 3-am inobenz-N-octadecyl-anilide -do Reddish-orange.

17 4-am1nobenz-N-dodecyl-anilide 2-naphthol-6:8-disulfonicacid Yellowish-orange. 18 4-aruinobenz-N-dodecyl-W-chloro-anido- Do.

lide.

19 4-aminobenz-N-dodecyl-anilide 20 3-aminobenz-N-dodecyl-anilide.

21 4-aminobenz-N-dodecyl-anilide 0 22 3-amino-4-methoxybenz-N dodecyl J) anilide.

23 4-aminobenz-N-dodecyl-anilide g4 4-a1n1inobenz-N-dodecyl-anilide 3-amino-4'methcxybenz-N dodecylanilide 25 3-arnino-methylbenz-N-dodecyl-ani- 4-aniiinobenz-N-dodecyl-anilide. o

lide. 4-aminobenz-N-dodecy1-2-toluidide 2-naphthol-3:6-disulfonic acid..- 1-naphtho1-3' disulfonic acid. l-naplithol disulfonic acid l-naphthol-tiz6-disulfonic acid 1-ecetyl-amino-8-naphthol-izfi-disulfonic acid Yellowish-red. 1-benzoylamino-8-naphthol-3zo-disulionic acid Bluish-red.

Reddish-orange.

Orange-brown. Reddish-orange. Scarlet.

1 p toluene sulfonyl amino 8 naphthol -B:6 Red.

disulfonic acid. l-acetylamine-8-naphtl1ol-3z6-d15ulfomc acid Dull red.

do Bright red.

Very bluish red.

l-phenoxy-acety1-amino-8-naphthol-3zfi-disultonic ac l-acetylamino-8-naphthol-3:6-disulionic acid--- Red.

.do Yellowish-red.

l-propionylamino-8-naplithol-3:fi-disulionlc acid. Red. 1-(2-chlorophenoxy-acetylamino)-8-naphthol-4:6- Yellowish-red.

disulfonic acid. l-(4-sulfophenyl)-5-pyrazolone-3-carboxylicacid. Reddish-yellow. l-benzoylamino-8-naphthol-4zfi-disulfonic acid.-- Bluish-red.

methyl-5-pyrazolone, X is a dodecyl radical, and Y is an aryl radical of the benzene series.

, As .many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. Dyestuifs represented by the formula:

in which X is a long chain aliphatic hydrocarbon radical having 10-20 carbon atoms, Y is a radical of the benzene series, and E is a component devoid of long chain ialiphatic hydrocarbon radicals O and from the group consisting of naphthol-disulfonic acids, naphthol-trisulfonic acids, N- acidyl- 1:8-amino-naphthol-disulfonic acids, and sulfoaryl-pyrazolones. H 2. The compounds of claim 1 in which X has from 10 to 16 carbon atoms.

3. Dyestuffs represented by the formula Y N=NE in which E is the radical of a 1-sulfo-pheny1-3- methyI-S-pyrazolone, X is a dodecyl radical, and Y is an aryl radical of the benzene series. (:3 4. Dyestufi's represented by the formula:

in which E is the radical of a 1-sulfo-phenyl-3- wherein X means a long chain aliphatic hydrocarbon radical of at least 10, and not more than 20 carbon atoms and Y means an aryl radical of the benzene series, with coupling components devoid of long chain aliphatic hydrocarbon radicals and which are from the class consisting of naphthol-dior tri-sulfonic acids, and N- acidyl-1:8- .amino-naphthol-disulfonic acids or sulfa-arylpyrazolones.

9. The compounds of claim 8 in which X has from 10 to 16 carbon atoms.

WILFRID HERBERT CLIFFE. ARTHUR HOWARD KNIGHT. 

